Carbamoyloximes



United States Patent Office 3,536,760 Patented Oct. 27, 1970 3,536,760CARBAMOYLOXIMES Linwood K.-Payne, Jr., Charleston, W. Va., and MathiasH. J. Weiden, Raleigh, NC, assignors to Union Carbide Corporation, acorporation of New York No Drawing. Original application Sept. 23, 1964,Ser. No. 398,744, now Patent No. 3,400,153, dated Sept. 3, 1968. Dividedand this application May 31, 1968, Ser.

Int. Cl. C07c 103/32 US. Cl. 260-561 6 Claims ABSTRACT OF THE DISCLOSURECompounds of the formula wherein R and R R can be hydrogen or loweralkyl, are useful as broad spectrum insecticides and miticides.

This application is a division of Ser. No. 398,744, filed Sept. 23, 1964now.U.S. Pat. No. 3,400,153 issued Sept. 3, 1968.

This invention relates to novel carbamoyloximes of a-electronegativelysubstituted carbonyl compounds. In a particular aspect, this inventionisrconcerned with novel urelectronegatively substitutedcarbamoylaldoximes and carbamoylketoximes. I

In addition to providing a novel class of carbamoyloximes thisinvention, affords pesticidal, e.g., insecticidal, miticidal, andnematocidal compositions having activity comparable or superior to themost effective commercially used materials. The miticidal action of thecarbamolyoximes encompassed herein is particularly important in that themite pests'are becoming increasing troublesome and difiicult to controlinasmuch as they are often resistant to general insecticides andunaffected by specific insecticides used to control a particular croppest.

Accordingly, an object of this invention is to provide novelcarbamoyloximes of a-electronegatively substituted carbonyl compounds.Another object is to provide novel a-electronegatively substitutedcarbamoylaldoximes and carbamoylketoximes. A further object is toprovide novel a-electronegatively substituted, a-methyl, a-substitutedN-methylcarbamoyloximes. A still further object is to provide novelcarbamoyloximes which possess pesticidal properties such asinsecticidal, nematocidal, and miticidal properties. Another object isto provide insecticidal, nematocidal, and miticidal compositionscomprising novel carbamolyoximes as disclosed herein. These and otherobjects will become apparent to those skilled in the art to which thisinvention pertains from the ensuing description thereof.

The novel carbamoyloximes of this invention can be represented byFormula I:

R and R are each individually hydrogen or lower alkyl, with at least oneof R or R being alkyl at all times, most preferably methyl; R R R R andR are each hydrogen or lower alkyl, most preferably methyl; and with theproviso that R and R and R and R can form a portion of a carbocyclicring containing from 4 to 7 ring carbon atoms. Preferably, when R to Rare alkyl, the alkyl group contains from 1 to 4 alkyl carbon atoms.

In the carbamoyloximes represented by Formula I, when R and R are bothlower alkyl, e.g., methyl, one or more of the hydrogen atoms on one onlyof the alkyl groups can be substituted by simple substituents such ascyano, nitro, methoxy, methylthio, halogens, trifluoromethyl, amido,formamido or thiocyanato. Also, when R and R and R and R form part of acarbocyclic ring, said ring can be substituted with one or more of theaforementioned simple substituents.

In a preferred aspect of this invention, the carbon atom attached tonitrogen through double bonds, is substituted with either hydrogen ormethyl (R =H or CH,), and the carbon atom alpha thereto, carries atleast one, and preferably two methyl groups (R and/ or R =CH while thecarbamate nitrogen is substituted with two radicals individuallyselected from the group consisting of hydrogen and lower alkyl, andpreferably hydrogen and methyl (R and/or R =H or CH and preferably wherethe total number of carbon atoms in such radicals together is not morethan ten. It has been found that those car bamoyloximes having at leastone methyl group on the carbon atom adjacent to the carbon atom attachedto the nitrogen atom through double bonds, and not more than two suchgroups, are particularly good pesticides, as to be disclosed herein.

The novel carbamoyloximes of this invention can be further representedby Formulae II and III:

wherein Y, R, R R and R are as hereinabove defined with reference toFormula I and R is alkyl. The carbarnyloximes specifically representedby Formula II can be referred to as the aldoximes of this invention andthose carbamoyloximes specifically represented by Formula HI as theketoximes of this invention. Both these oximes are contemplated aswithin the preview of this invention.

Particularly preferred carbamoyloximes of this invention can berepresented by the aldoximes of Formula IV and the ketoximes of FormulaV:

wherein Y is as defined hereinabove with reference to Formula I.

Representative carbamoyloximes encompassed within this inventioninclude, among others, the carbamoyloximes, the N-methylcarbamoyloximes,the N,N-dimethylcarbamoyloximes, the N-ethylcanbamoyloximes, andN-allylcarbamoyloximes of the following aldehydes and ketones:2-formamido-Z-methylpropionaldehyde,Z-acetamido-Z-methylpropionaldehyde, 2-(-N'methylformamido)-2-methylpropionaldehyde, 2-formamido-2-methyl-3-butanone, 2-acetamido-2-methyl-3-butanone.

The carbamoyloximes of this invention may be prepared, for example, asfollows:

(A) Oxime.-The nitrosochloride dimer is reacted with a slight excess ofsodium nitrite '(or sodium cyanide) (1.1 mole of sodium nitrite perequivalent of chlorine) by adding the dimer to a suspension of sodiumnitrite in dimethylsulfoxide. The addition is conducted with rapidagitation and maintaining a reaction temperature of 20-65 C. forsufiicient time to insure reaction (usually 2-3 hours although up to 60hours may be required), After filtering the reaction mixture to removesodium chloride, the solvent is removed by stripping under reducedpressure. The residue product is dissolved in an inert water-insolublesolvent such as ether, the ether solution is washed with 3 water toremove any remaining dimethylsulfoxide and then the ether is removed bystripping under reduced pressure. The residue oxime may 'be purified byrecrystallization. The nitrosochloride dimers used to prepare the oximeprecursors are prepared by the addition of nitrosyl chloride to asuitable olefin by well-known procedures for example, as taught in J.Gen. Chem., (U.S.S.R.), 22, 2175 (1952).

(B) N-methyl carbamate.-To a solution of the oxime in an inert solvent,if desired, such as diethyl ether or acetone, is added an equimolarquantity of methyl isocyanate. The reaction is conducted, at the boilingpoint of the reaction mixture and can be carried out in the presence ofa catalytic amount of well-known catalysts such as dibutyltin diacetateor di-2-ethylhexanoate, pyridine, triethylamine, or1,4dia-zabicyclo[2.2.2] octane. After sufiicient time, usually about 3-6hours, for the reaction to be completed, the solvent, if employed, isremoved by stripping under reduced pressure, and the crude product maybe purified by recrystallization. This procedure works well with orwithout a catalyst and additional solvent is not required as methylisocyanate itself can serve as solvent.

The synthetic route for preparing the carbamoyloximes of this inventionfrom the corresponding oximes involving 0 the addition of methylisocyanate can be illustrated as follows:

wherein Y and R are as hereinabove defined with reference to Formula I.

Reaction (1) can be carried out by contacting the oxime (VIII) withmethyl isocyanate in an inert organic solvent, and preferably in thepresence of a tertiary amine or organotin catalyst. The reaction may beefiected at temperatures ranging from about 10 C. to about 130 C., andis preferably carried out between room temperature and C. Generally,temperature in excess of about C. are to be avoided in view of thetemperature sensitivity of the product carbamoyloxime. The operatingpressure may range from about 1 atmosphere to about 10 atmospheres,preferably from about 2 to about 3 atmospheres, and is dependent uponthe concentration and vapor pressure of the volatile isocyanate at thereaction temperature. The inert organic solvents that can be employed inthe reaction, when additional solvent is desired, are those inert toisocyanates in general, i.e., those free of radicals such as hydroxy oramino radicals. Illustrative solvents are aliphatic and aromatichydrocarbons, such as hexane, heptane, octane, benzene, toluene, and thelike, and ethers such as diethyl ether, diisopropyl ether, and the like.Other solvents which can be employed include ketones such as methylethyl ketone and acetone; nitriles such as acetonitrile; and halocarbonssuch as chloroform and methylene chloride. The ketones and acetonitrileare the solvents of preference. The reaction is preferably carried outin the presence of a tertiary amine or organotin catalyst. The termorganotin catalyst as used herein is meant to refer to such compounds asdibutyltin diacetate, dibutyltin dichloride, dibutyltin dimethoxide,dibutyltin dilaurate, dibutyltin maleate, dibutyltindi-2-ethylhexenoate, stannous octanoate, stannous oleate, and the like.Generally, amounts of said catalyst from about 0.1 to about 1.0 weightpercent of the starting material comprised of methyl isocyanate and theoxime are sufiicient. The mol ratio of methyl isocyanate to oxime ispreferably an equimolar amount or excess of methyl isocyanate so as toinsure that the oxime is completely reacted. The reaction time may varyfrom about 5 minutes to about 7 days, but normally when operating in thepreferred temperature range, reaction times of from about one-half hourto about five hours are sufiicient for complete reaction. Thecarbamoyloxime product formed, either a solid or oily liquid, can berecovered from the reaction mixture by means known to the art, e.g., byvacuum distillation to drive off solvent and excess isocyanate.

The carbamoyloximes of this invention also may be prepared by thereaction of the corresponding oxime with phosgene to form thechloroformate which, in turn, is racted with amines, for example,ammonia to give the carbamoyloxime or methylamine to give theN-methylcarbamoyloxime or dimethylamine to give theN,N-dimethylcarbamoyloxime. The synthesis is illustrated by thefollowing general reaction scheme:

wherein Y and R are as hereinabove defined with reference to Formula Iand R is either hydrogen or lower alkyl.

The oxime precursors (X), may be prepared as noted hereinabove from thenitrosochloride dimer. In step (2),

a solution of the phosgene in, e.g., toluene or diethyl ether isconveniently added dropwise to a solution of the oxime compound (X) intoluene or diethyl ether in the presence of an HCl acceptor such asdimethyl aniline. (The dimethyl aniline is usually in the phosgenesolution.) The reaction can be carried out at from 30 C. to about 40 C.but will generally be found to proceed most advantageously between C.and room temperature. Below 0 C. the reaction is somewhat sluggish andif the temperature is allowed to rise substantially above 40 C.,considerable quantities of nitrilefrom the dehydration of the aldoximecompound will appear in the reaction mixture. The reaction is slightlyexothermic so that some external cooling is usually necessary tomaintain the temperature within the desired range. The reaction mixturecan be washed with water to remove the amine hydrochloride and theorganic layer containing the chloroformate can be used for furtherreactions. The addition of amine step (3) above, is carried out in thepresence of solvents for the amine, such as water, dioxane, toluene, orchloroform, at temperatures between about --40 C. and about 80 C., andpreferably below about 40 C. inasmuch as the reaction precedes smoothlyeven at low temperatures and is so rapid above 40 C. that loss of lowboiling amines may occur and some decomposition may take place.

The following examples are illustrative:

EXAMPLE I N-methylcarbamoyloxime 2-forn1amido- 2-methyl-3-butanoneZ-formamido 2 methyl 3 butanone oxime (8 gms.; 0.056 mole) was dissolvedin 100 ml. of anhydrous ethyl ether and treated with methyl isocyanate(3.5 gms.; 0.062 mole) and two drops of dibutyltin diacetate. Afterstanding for sixteen hours the reaction mixture was filtered and thecrystals washed with ethyl ether. 6 grams (53 percent yield) ofZ-formamido 2 7 methyl 3 butanone N-methylcarbamoyloxime was obtained,M.P. 118- 120 C.

Analysis.-Calcd. for C H N O (percent): C, 47.7; H, 7.5; N, 20.9. Found(percent): C, 47.4; H, 7.3; N, 20.7.

Infrared: NH at 2.94 1, 3.05;, 655 and 665 carbamate 0 0 at 5.80 amide(:0 at 597 1.; carbonate C-O at 8.03 and C=N-O at 10.52 2.

EXAMPLE II 2-formamido-2-methylpropionaldehyde N-methylcarbamoyloxime2-formamido-2-methyloproprionaldehyde oxime was obtained by allowingZ-amino-Z-methylpropionaldehyde oxime (12.6 g.; 0.124 mole) to react forthree hours at 35 C. with vinyl formate (10 g.; 0.14 mole) in 200 ml. ofanhydrous acetone. The solvent was evaporated under reduced pressure.The residual 2-formamido-2-methylpropionaldehyde oxime was dissolved in200 ml. of chloroform and treated with methylisocyanate (7.6 g.; 0.134mole) and 1 drop of dibutyltin diacetate. After two hours at 35 C. thesolvent was evaporated under reduced pressure and the residue wasstirred with 150 ml. of ethyl acetate. The precipitate was collected byfiltration washed with petroleum ether and dried. 2-formamido-2-methylpropionaldehyde N-methylcarbamoyloxime, M.P. 113-1 C., wasobtained in 52 percent yield.

6 Analysis.-Calcd. for C7H13N303 (percent): C, 44.9; H, 7.0; N, 22.7.Found (percent): C, 44.6; H, 7.2; N, 22.4.

EXAMPLE III 2-(N'-methylformamido) -2-methylpropiona1dehydeN-methylcarbamoyloxime Z-(N-methylformamido) 2 methylpropionaldehydeoxime (4 'gms.;'0.027 mole) was dissolved in 200 ml. of anhydrousacetone and heated at 40 C foreight hours with methyl isocyanate (1.7gms.; 0.3 mole). The solvent was stripped in, vacuo and the residueheated to 50/3 mm. 2-N-methylformamido) 2-methyl-proprioaldehydeN-methylcarbamoyloxime was obtained as a viscous oil weighing 5 gms. (92percent yield).

Analysis.-Calcd. for C H N O (percent): C, 47.8; H, 7.5; N, 20.9. Found(percent): C, 47.6; H, 8.0; N, 20.4.

Infrared: Carbamate NH, 3.0,u and 6.6 carbamate C=O, 5.82m carbamateC-O, 8.05 1; =NO, 10.55 amide C=O, 6.05,u.. Weak CEN impurity noted at4.48;.

EXAMPLE IV 2-acetarnido-2-methylpropionaldehyde N-methylcarbamoyloxime ii n OH;-iI-NH-00H=No-o-NHCH= Z-acetamido-Z-methylpropionaldehyde oximewas treated with methyl isocyanate in chloroform solution to produceZ-acetamido 2 methylpropionaldehyde N-methylcarbamoyloxirne in 46 percent yield; M.P. 143l45 (ethyl acetate).

Analysis.-Calcd. for C H N O (percent): C, 47.7; H, 7.5; N, 20.9. Found(percent): C, 48.1; H, 7.8; N, 21.1. 1

Infrared: Carbarnate (3 0 at 5.78,u; amide C=O at 6.08 11; carbamate C-Oat 7.93 and C=N--O at 10.7

EXAMPLE V 2-acetamido-2-methyl-3-butanone N -methylcarbamoyloxime2-acetamido-2-methyla3rbutanone oxime (4 gms; 0.025 mole) was dissolvedin 70 ml. of dimethylformamide and treated with methyl isocyanate (1.7gms.; 0.03 mole) and two drops of dibutyltin diacetate for sixty hoursat room temperature. The solvent was evaporated under reduced pressureand the residue treated with ml. of ether. The resulting solid wascollected by filtration, washed with ether and dried. There was obtained5 gms. (93 percent yield) of 2-acetamido-2-methyl-2-butanoneN-methylcarbamoyloxime, M.P. 100-103 C.

Analysis.-Calcd. for C H N O (percent): C, 50.2; H, 8.0. Found(percent): C, 48.6; H, 8.4.

Infrared: NH at 2.95;, 3.04p, 6.411., and 6.65 carbamate 0 0 at 5.8amide C=O at 6.08p.; carbamate C-O at 8.08 and C=N at 10.54

The carbamoyloximes of this invention show particular promise aspesticides. They are particularly useful in agricultural applications tocombat undesirable organisms which adversely elfect plant life. Thecarbamoyloximes disclosed herein have been shown to be particularlyactive as insecticides, nematocides and miticides.

2-formamido 2 methylbutan-3-one -N methylcarbamoyloxime has exhibitedfor example, significant oxic properties to the two-spotted mite. Thecarbamoyloxime,

acetone, addition of an emulsifier, and the serial dilution with water.Paired seed leaves, excised from Tendergreen bean plants, were dipped inthe test formulations until thoroughly wetted, excess liquid beingremoved by gentle shaking. While the leaves were drying in a ventilatedhood, wilting was prevented by placing the stems in water. When dry, thepaired leaves were separated and each one was placed in a 9-centirneterPetri dish lined with moistened filter paper. Four randomly selectedlarvae were introduced into each dish and the dishes were closed. The

TABLE I.BIOLOGICAL ACTIVITY OF N-METHYL CARBAMOYLOXIMES 1 LDsu, p.p.m.acre) Compound Name BA M AW MBB HF N EMA Example:

1 2-l'ormamido-2-methyl-3-butanone N-methylcarbamovloxime 100 30 1, 000100 120 2...- 2-f01mamido-2-methylpropionaldehydeN-methylcarbarnoyloxime 6 3 150 2 8 3,2-(N-methylformamido)-2-rnethylpr0pi0naldehyde N-methylcarbamolyoximen12 16 1, 000 100 10 19 4 2-acetan1ido-2-methylpropionadlehydeN-methylcarbamqyloxlme 12 17 1, 000 100 4 50 52-acetamido-2-rnethyl-B-butanone N -methylcarbam0y1 mm 100 400 1, 000100 00 BA=Bean Aphid; M=Two-Spotted Mite; AW=Southern Armyworm;MBB=Mexiean Benn Beetle; HF=House Fly NEMA= t;

Nematode.

NOTE.ED3=& given concentration of N-methylcarbarnoyloxirne whichwillelicit a rating of 3 (light gelling) on a scale of 1 to 5. As us d hi the term ED; is for all practical purposes synonymous with the termLDso; but in pounds/acre.

The carbamoyloximes of this invention have been tested for activityagainst the following representative pests: bean aphid, armyworm,Mexican bean beetle, housefly, two-spotted mite, and root-knot nematode.

The tests employed and shown in the tables herein are as follows:

APHID FOLIAGE SPRAY TEST Adults and nymphal stages of the bean aphid (Aphz's fabae Scop.), reared on potted dwarf nasturtium plants at 6570 F.and 50-70 percent relative humidity, constituted the test insects. Fortesting purposes, the number of aphids per pot was standardized to100-150 by trimming plants containing excess aphids. The test compoundswere formulated by a standard procedure which involved solution inacetone, addition of an emulsifier, and then serial dilution with water.The potted plants (one pot per concentration tested), infested with 100150 aphids, were placed on a revolving turntable and sprayed with 100-110milliliters of test compound formulation by use of a DeVilbiss spray gunset at p.s.i.g. air pressure. This application, which lasted 30 seconds,was sutficient to wet the plants to run-off. As a control, 100-110milliliters of a Water acetone emulsifier solution containing no testcompound were also sprayed on infested plants. After spraying, the potswere placed on their sides on a sheet of white standard mimeograph paperwhich had been previously ruled to facilitate counting. Temperature andhumidity in the test room during the 24-hour holding period were 65-70"F. and -70 percent, respectively. Aphids which fell onto the paper andwere unable to remain standing after being uprighted were considereddead. Aphids remaining on the plants were observed closely for movementand those which were unable to move the length of the body uponstimulation by prodding were considered dead.

After correcting for natural mortality by means of Abbotts formula, theLD in p.p.m. was estimated by plotting the logarithm of theconcentration versus probit of the mortality in the usual manner.

ARMYWORM LEAF DIP TEST Larvae of the southern armyworm (Prodeniaeridania, Cram), reared on Tendergreen bean plants at a temperature of80:5 F. and a relative humidity of 5015 percent, constituted the testinsects. The test larvae Were removed from the colony and held withoutfood for four hours prior to the test. The test compounds wereformulated by a standard procedure which involved solution in closeddishes were labeled and held at -85 F. for three days. Although thelarvae could easily consume the whole leaf within twenty-four hours, nomore food was added. Larvae which were unable to move the length of thebody, even upon stimulation by prodding, were considered dead. Aftercorrecting for natural mortality by means of Abbotts formula, the LD inp.p.m. was estimated by plotting the logarithm of the concentrationversus probit of the mortality in the usual manner.

MEXICAN BEAN BEETLE LEAF DIP TEST Third instar larvae of the Maxicanbean beetle (Epilac/ma vau'iveslis, Muls.), reared on Tendergreen beanplants at a temperature of 80:5" F. and 501-5 percent relative humidity,were the test insects. The test compounds were formulated by a standardprocedure which involved solution in acetone, addition of an emulsifier,and then serial dilution with water. Paired seed leaves excised fromTendergreen bean plants were dipped in the test formulation untilthoroughly wetted, excess liquid being removed by gentle shaking. Whilethe leaves were drying under a hood, wilting was prevented by placingthe stems in water. When dry, the paired leaves were separated and eachwas placed in a 9-centimeter Petri dish lined with moistened filterpaper. Four randomly selected larvae were introduced into each dish, andthe dishes were closed. The closed dishes were labeled and held at atemperature of 80i5 F. for three days. Although the larvae could easilyconsume the leaf within 24 to 48 hours, no more food was added. Larvaewhich were unable to move the length of the body, even upon stimulation,were considered dead. After correcting for natural mortality by means ofAbbotts formula, the LD in p.p.m. was estimated by plotting thelogarithm of the concentration versus probit of the mortality in theusual manner.

FLY BAIT TEST Four to six day old adult house flies (Musca domestica,L.), reared according to the specifications of the Chemical SpecialtiesManufacturing Association (Blue Book, MacNair-Dorland Co., N.Y., 1954:pages 243-244, 261) under controlled conditions of 80:5 F. and 50:5percent relative humidity, were the test insects. The flies wereimmobolized by anesthetizing with carbon dioxide and twenty-fiveimmobilized individuals, males and females, were transferred to a cageconsisting of a standard food strainer about five inches in diameterwhich was inverted over blotting paper. The test compounds wereformulated by a standard procedure which involved solution in ace- 9.tone, addition of an emulsifier and then serial dilution with water.Fifteen milliliters of the test formulation were added to a soufil cupcontaining a one-inch square of an absorbent pad. This bait cup wasintroduced and centered on the blotting paper under the food strainerprior to admitting the flies. The caged flies were allowed to feed onthe bait for twenty-four hours, at a temperature of 80:5 F. and therelative humidity of 50:5 percent. Flies which showed no sign ofmovement on prodding were considered dead. After correcting'for naturalmortality by means of Abbotts formula, the LD in p.p.m. was estimated byplotting the logarithm of the concentration versus probit of themortality in the usual manner.

MITE FOLIAGE SPRAY TEST Adults and nymphal stages of the two-spottedmite (Tetranychus telarius L.), reared on Tendergreen bean plants at80:5 F. and 50:5 percent relative humidity, were the test organisms.Infested leaves from a stock culture were placed on the primary leavesof two bean plants six to eight inches in height, growing in atwo-anda-half inch clay pot. 150-200 mites, a sufiicient number fortesting, transferred from the excised leaves to the fresh plants in aperiod of twenty-four hours. Following the twenty-four hour transferperiod, the excised leaves were removed from the infested plants. Thetest compounds were formulated by a standard procedure which involvedsolution in acetone, addition of an emulsifier, and then serial dilutionwith water. The potted plants (one pot per concentration) were placed ona revolving turntable and sprayed with 100-110 milliliters of testcompound formulation by use of a DeVilbiss spray gun set at 40 p.s.i.g.air pressure. This application, which lasted 30 seconds, was sufficientto wet the plants to runoff. As a control, 100410 milliliters of a watersolution containing acetone and emulsifier in the same concentrations asthe test compound formulation, but containing no test compound, werealso sprayed on infested plants. The sprayed plants were held at 80:5 F.and 50:5 percent relative humidity for six days, after which a mortalitycount of motile forms was made. Microscopic examination for motile formswas made on the leaves of the test plants. Any individual which wascapable of locomotion up'on prodding was considered living. Aftercorrecting for natural mortality by means of Abbotts formula, the LD inp.p.m. was estimated by plotting the logarithm of the concentrationversus probit of the mortality in the usual manner.

MITE SYSTEMIC TEST Adults and nymph stages of the two-spotted mite (Tetranychus telarius L.), reared on Tendergreen bean plants at 80:5 F.and 50:5 percent relative humidity, were the test organisms. Infestedleaves from a stock culture were placed on the primary leaves of twobean plants six to eight inches in height, growing in a two-and-a-halfinch clay pot. 150-200 mites, a sufficient number for testing,transferred from the excised leaves to the fresh plants in a period oftwenty-four hours. The test compounds were formulated by a standardprocedure of solution in acetone, addition of an emulsifier, and thenserial dilution with water. The potted plants were placed in 4 02. papercontainers, and thirty milliliters of the test formulation were drenchedinto the pot containing the infested plants. The treated plants wereheld for fortyeight hours at 80:5 F. and 50:5 percent relative humidity.After the forty-eight hour holding period, microscopic examination formotile forms was made on the leaves of the test plants. Any individualcapable of locomotion upon prodding was considered living. Aftercorrecting for natural mortality by means of Abbotts formula, the LD inp.p.m. was estimated by plotting the logarithm of the concentrationversus probit of the mortality in the usual manner.

10 NEMATOCIDB TEST Infective migratory larvae of the root-knot nematode(Meloidogyne incognita, var. acrita), reared in the greenhouse on rootsof Coleus plants constituted the test organism. Infected Coleus plantswere removed from the culture and the roots were chopped very finely.AIsma'll amount of these choppings was added to a pint Mason jarcontaining approximately cubic centimeters of soil. The jar was cappedand incubated for one week at room temperature. During the incubationperiod eggs of the nematode hatch and the larval forms migrate into thesoil. The test compounds were formulated by a standard procedure ofsolution in acetone, addition 'of an emulsifier, and the serial dilutionwith water. Ten milliliters of the test formulation were added to eachof two jars for each dose tested. Thus each jar contained 25 milligramsof test compound, an amount roughly equivalent to 75 pounds per acre.Following the introduction of the test formulation, the jars were cappedand the contents thoroughly mixed on a ball mill for five minutes. Thejars remained capped at room temperature for 48 hours whereupon thecontents were transferred to 3-inch pots. These pots were then seededwith cucumber as an indicator crop and placed in thegreenhouse wherethey were cared for in the usual fashion for approximately three week's.The cucumber plants were removed from the pots and the soil was washedfrom the roots. The amount of galling was determined by visualinspection and rated according to the following designations:

5=no galling; perfect control 4=very light galling 3=light galling2=moderate galling l=severe galling, equal to untreated plants Thecontrols exhibited no pesticidal activity.

The carbamoyloximes contemplated in this invention may be applied asinsecticides, acaracides and nematocides according to methods known tothose skilled inlthe' art. Pesticidal compositions containing thecompounds as the active toxicant will usually comprise a carrierand/ordiluent, either liquid or solid.

Suitable liquid diluents and/or carriers include}. water, petroleumdistillates, or other liquid carriers with or without surfaceactiveagents. Liquid concentrates' rnay be prepared by dissolving one ofthese compounds a nonphytotoxic solvent such as acetone, xylennitrobenzene and dispersing the toxicants in water the aid of suitablesurface active, emulsifying and dispersl mg agents.

The choice of dispersing and emulsifying agent and; amount employed isdictated by the nature of thedoni g position and the ability of theagent to facilitate] the dispersion of the toxicant. Generally, it isdesirable to use as little of the agent as is possible, consistent withthe desired dispersion of the toxicant in the spray so that rain doesnot re-emulsifyithe toxicant after it is applied to the plant and washit off the plant. Nonionic, anionic, or cationic dispersing andemulsifying agents may be employed, for example, the condensationproducts of alkylene oxides with phenol and organic acids, alkyl arylsulfonates, complex ether alcohols, quaternary ammonium compounds, andthe like.

In the preparation of wettable powder or dust or granulatedcompositions, the active ingredient is dispersed in and on anappropriately divided solid carrier such as clay, talc, bentonite,diatomaceous earth, fullers earth, and the like. In the formation of thewettable powders the aforementioned dispersing agents as well aslignosulfonates can be included.

The required amount of the toxicants contemplated herein may be appliedper acre treated in from 1 to 200 gallons or more of liquid carrierand/or diluent in from about 5 to 500 pounds of inert solid carrierand/or diluent. The concentration in the liquid concentrate will usuallyvary from about 10 to 95 percent by weight and in the solid formulationsfrom about 0.5 to about 90 percent by weight. Satisfactory sprays,dusts, or granules for general use contain from about A to 15 pounds ofactive toxicant per acre.

The pesticides contemplated herein prevent attack by insects, mites, andnematodes upon plants or other material to which the pesticides areapplied and they have high residual toxicity. With respect to plantsthey have a high marginof safety in that when used in suflicient amountto kill or repel the insects, they do not burn or injure the 'plant, andthey resist Weathering which includes wash-off caused by rain,decomposition by ultra-violet light, oxidation, or hydrolysis in thepresence of moisture or, at least, such decomposition, oxidation, andhydrolysis as would materially decrease the desirable insecticidalcharacteristic of the toxicants or impart undesirable characteristics,for instance, phytotoxicity, to the toxicants. The toxicants are sochemically inert that they are compatible with substantially and otherconstituents of the spray schedule, and they maybe used in the soil,upon the seeds, or the roots of plants without injuring either the seedsor roots of plants, yet by inhibition or root uptake they will kill thepests feeding thereon.

It also has been found that carbamoyloximes of this invention can besynergized with a wide-variety of compounds except acidic and phenoliccompounds or compounds readily metabolized thereto. Little or nosynergism has been observed with compounds highly active as pesticidesby themselves. Compounds showing moderate to poor pesticidal activityyet possessing good anticholinesterase properties are most likely to besynergized. The carbamoyloximes herein can "be synergized withsynergists such as piperonyl butoxide, propyl isome, sesamex, sulfoxide,methylenedioxyphenyl compounds, and2-(3,5-dichloro-Z-biphenylyloxy)triethylamine. In general, thosesynergists which are known to synergize the carbamate pesticides alsocan be used to synergize the carbarnoyloximes of this invention such asthose synergists disclosed in US. Pats. Nos. 2,904,463; 2,904,464; and2,904,465, incorporated herein by reference.

A concentration range of from about 20 parts synergist to about 1 partcarbamoyloxime through 1 part synergist to 5 parts carbamoyloxime areexpected to give a synergistic elfect.

What is claimed is:

1. Carbamoyloxime compounds of the formula:

wherein R is lower alkyl and R R R R R and R are hydrogen or loweralkyl.

2. Carbamoyloxime as claimed in claim 1 wherein the compound is2-formamido-2-methy1propionaldehyde N- methylcarbamoyloxime.

3. Carbamoyloxime as claimed in claim 1 wherein the compound is2-formamido-2-methyl-3 butanone N-methylcarbamoyloxime.

4. Carbamoyloxime as claimed in claim 1 wherein the compound is2-(N-methylf0rmamido)-2-methylpropionaldehyde N-methylcarbamoyloxime.

5. Carbamoyloxime as claimed in claim 1 wherein the compound is2-acetamido-2-methylpropionaldehyde N- methylcarbamoyloxime.

6. Carbamoyloxime as claimed in claim 1 wherein the compound isZ-acetamido-Z-methyl-B-butanone N-methyl- Carbamoyloxime.

References Cited UNITED STATES PATENTS 3,400,153 9/1968 Payne et a1260-566 ALEX MAZEL, Primary Examiner R. V. RUSH, Assistant Examiner US.Cl. X.R. 424-320

